Growth of piezoelectric crystals by Czochralski method D. Cochet-Muchy To cite this version: D. Cochet-Muchy. Growth of piezoelectric crystals by Czochralski method. Journal de Physique IV Proceedings, EDP Sciences, 1994, 04 (C2), pp.C2-33-C2-45. 10.1051/jp4:1994205. jpa-00252473 HAL Id: jpa-00252473 https://hal.archives-ouvertes.fr/jpa-00252473 Submitted on 1 Jan 1994 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. JOURNAL DE PHYSIQUE IV Colloque C2, supplBment au JournaI de Physique 111, Volume 4, fkvrier 1994 Growth of piezoelectric crystals by Czochralski method D. COCHET-MUCHY Crismatec, Usine de Gikres, 2 me des Essarts, 386610 Gi.?res, France Abstract : The Czochralski method is one of the most widely used industrial technique to grow single-crystals, since it applies to a very large range of compounds, such as semiconductors, oxides, fluorides, etc... Many exhibit piezoelectric properties and some of them find applications in Surface-Acoustic-Waves or Bulk- Acoustic-Waves devices. That explains the large amount of work made on the development of the corresponding growth processes and the high levels of production achieved in the world today. We will review the basic principle, main features and parameters of the Czochralski method, and the configuration which is used by Crismatec. Then we will discuss in more details the growth parameters for the two piezoelectric crystals that we are producing, LiNb03 and LiTaO3, and present the state-of-the-art for both crystals : pulling axis, diameter and quality. We will also discuss some preliminary results on the growth of the new La3Ga5SiOlg langasite crystal. 1. INTRODUCTION The need for piezoelectric crystals has been raising since around 20 years due to their use in several mass-produced electronic equipments : TV, watches, radio receivers and communication systems, etc ... Among their advantages, they allow low-cost, compact-size and reliable devices to be manufactured, such as frequency filters, resonators and oscillators. Mainly the crystals having the highest electro-mechanical coupling coefficient and the lowest temperature coefficient are interesting candidates. The materials which are known to have one of these properties or which exhibit a good compromise [I] are shown in Table I. The growth of these compounds as large single-crystals is the first requisite to their use by the electronic manufacturers. For this reason, the growth techniques have been widely investigated, and, when possible, the Czochralski technique was used as it is one of the most convenient method for industrial production. Undoubtdedly, the best accomplishments of these efforts towards the growth of piezoelectric crystals by Czochralski method were obtained with LiNb03 and LiTa03. They are now on a large scale produced and processed into wafers for Surface-Acoustic-Waves (SAW) devices, mainly in Japan, but also in US and Europe. More recently it appeared that the promising La3Ga5SiO14 could also be grown with good results [2]. Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jp4:1994205 JOURNAL DE PHYSIQUE IV After a discussion of the main issues associated with the Czochralski method, we will focus on our experience in growing these piezoelectric crystals. Table I Characteristics of some piezoelectric crystals Crystal Cut-plane Electromechanical Temperature Propagation Growth coupling coefficient mode method coefficient (ppm/OC) ~2 (%) SAW hydrothermal BAW A1PO, 170' rotated SAW X Li2B4O7 X Czochralski Li NbO, 128' rotated Y LiTaO, X Pb2KNb5OI5 X La3Ga5SiOI4 - Y BAW 2. THE CZOCHRALSKI METHOD 2.1 Basic grincige The Czochralski method is a crystal pulling technique from the melt. The process is based on a liquid-solid phase transition driven by a seed crystal in contact with the melt. Basically, the seed is to be considered as a heat sink, by which the latent heat of solidification escapes, and as a nucleation center : the solidified fraction at the surface of the seed will reproduce its single-crystal structure. By raising the seed slowly, a crystal is "pulled" from the melt. Decreasing the melt temperature makes the crystal diameter increasing and vice versa. A sketch of this process is shown in Fig. 1. 2.2 Limitations 2.2.1. Techno1 ogi cal considerations When bringing this relatively simple process into operation, one have to solve several major technological problems : (1) finding a crucible which is compatible with the melt to crystallize (higher melting point and chemical stability) and the surrounding atmosphere. (2) selecting insulator materials acting as a thermal barrier all around the crucible and controlling the thermal field in the crystallization area. (3) finding a heating source compatible with the environment described above. (4) controlling the diameter of the growing crystal. 2.2.1.1. Crucible For oxide crystals, noble metals give the best compromise between chemical stability and mechanical strength. Platinum, Platinum-based or Iridium crucibles are used, depending on the melting point of the oxides (T,). When a choice is possible between several crucible materials, cost is generally the key factor. Total cost includes the raw metal, the manufacturing of the crucible, the metal loss and repairing during the lifetime of the crucible. Strong variations of some of these elements occurs from time to time and can change the optimum choice. Table I1 shows the possible crucibles for the piezoelectric crystals discussed in this article. Table I1 Crucibles used for some piezoelectric oxides - - ------ ---- Oxide Tm (") Crucible Tm ("C) Atmosphere Platinum preferably oxdiz ing 1650 Iridium 2454 neutral Platinum-Rhodium 1930 preferably neutral (- 30 %) 1470 Platinum 1769 preferably neutral The choice of the pulling atmosphere is a compromise between what is preferable for the crystal and what is preferable for the crucible. According to the crystal chemistry, it is of course preferable to pull an oxide under an oxidizing atmosphere, but it is not a prerequisite, since oxygen vacancies which can formed during pulling under neutral atmosphere are generally removed with an oxidizing post-annealing. Often, either problems such as metallic impurities, inclusions into the crystal (e.g. Rh, see [31) or the stability of the crucible materials at the operating temperature determined the atmosphere. When iridium crucibles are used, a neutral atmosphere is required to avoid the volatilization of IrO2. 2.2.1.2. Insulators The refractory materials which surround the crucible are commonly alumina-silica, pure alumina or zirconia ceramics, depending on the operating temperature. The design of these ceramics is a major feature of the pulling process for a given crystal, since it determines the thermal gradients (see 2.4.3). 2.2.1.3. Heating source They are two ways of generating the heat to melt the compound inside the crucible : resistance heating and induction heating. Resistance heating is commonly used up to 1400°C with the advantages of a very universal heating technique : low-cost, reliability and standardization, both for the heating elements and the power control equipments. In addition the distribution of the hot zones, easily JOURNAL DE PHYSIQUE IV controlled, enables to get high uniformity of the thermal field (i.e. low gradients). Induction heating uses a r.f. generator to generate r.f. currents into a coil surrounding the crucible, which acts as a susceptor. Obviously, the crucible must be conductive, which is the case with noble metals. Heat is generated into a "skin depth" at the outer surface of the crucible. This makes the thermal field control more difficult. In order to get the desired gradients, one should pay more attention to the design of the ceramics and, sometimes, extra-heaters ("after-heater1') must be introduced, such as secondary metallic susceptors (or reflectors) over the crucible, or resistance heated zones. The position of the crucible with respect to the coil also plays a significant role to (see 2.4.3). Contrary to the resistance heating, induction heating is not temperature limited. Moreover, the environment of the crucible is preserved very clean. Therefore, crystals with very high level of purity can be produced. 2.2.1.4. Diameter control The diameter control is required to obtain crystals as close to the dimensions of the final products as possible. We said above that the diameter fluctuations are due to variations of the melt temperature. The way of correcting the melt temperature is obviously to adjust the power of the heating source. Theorically, with a correctly designed pulling furnace, no variation of the heating power gives no variation of the diameter. In practice, this situation is ideal, and designers should try to reach it, but, as usual in reality, full stability does not exist. Also, over a long time period, a constant heating power will make the melt temperature regularily increase (i.e. the diameter decrease) since the quantity of compound to be kept molten decreases while crystallization is running. Measuring the melt temperature and using a feedback regulation system to keep up a constant temperature (setpoint) is a way to control the diameter. However, this method, easy to apply in the case of resistance furnace, is not the most routinely used. One generally prefers control systems which take directly into account a diameter setpoint. Such systems are using optical sensing or weighing techniques. The latter is nowadays the most commonly used as it is rather simple to put in operation and reliable whatever the pulling configuration is.